Use of hydroxyanthraquinones for the coloration of human keratin fibres

ABSTRACT

Use of hydroxyanthraquinones for the coloration of human keratin fibres, and process and composition in which they are used. 
     The composition contains, in a cosmetically acceptable medium, at least one hydroxyanthraquinone of the formula: ##STR1## in which R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7  and R 8  independently of one another denote a hydrogen atom, a hydroxyl group, an alkyl group, an alkyl group substituted, for example, by a hydroxyl, amino or acyl group, an alkoxy group, a nitro group, a halogen group, a group SO 3  H, CHO, CO 2  H or SO 3  Na, or a group --CO 2  R&#39;, in which R&#39; denotes alkyl or an alkali metal, with the proviso that: at least two of the groups R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7  and R 8  denote hydroxyl, and that if R 1  and R 2  denote OH, R 5 , R 6 , R 7  and R 8  denoting hydrogen, then at least one of the two groups R 3  and R 4  is different from hydrogen, or alternatively if R 1  and R 3  denote OH, R 2  and R 4  denoting hydrogen and one or two of the substituents R 5 , R 6 , R 7  and R 8  denoting hydroxyl, then at least one of the substituents R 5 , R 6 , R 7  and R 8  is different from hydrogen, alkyl or halogen.

This is a continuation of application Ser. No. 353,003, filed Feb. 26,1982, now abandoned.

The present invention relates to the use of hydroxyanthraquinones forthe coloration of human keratin fibres, and in particular living hair,and to the coloration processes and the dyeing compositions in whichthese compounds are used.

Aminoanthraquinone derivatives have already been used for the directcoloration of the hair, see, for example, French Pat. Nos. 1,422,016,1,391,675, 1,401,163, 1,379,649, 1,430,091 and 1,574,275. Furthermore,it has already been proposed to use certain hydroxyanthraquinones,described, in particular, in French Pat. No. 2,106,264 to colour thehair.

We have now discovered that, surprisingly, a particular class ofhydroxyanthraquinones makes it possible to obtain coloration of humanhair directly, even at ambient temperature. These compounds give rise todyeings having a good resistance to light, washing, adverse weatherconditions and perspiration. Furthermore, they make it possible toobtain a very wide variety of colorations.

These dyestuffs also have the advantage of being very stable in solutionin the cosmetic media normally used for this type of dyeing.

Moreover, thse dyestuffs generally have a low toxicity as well as a goodaffinity, making them particularly suitable for dyeing of human hair.

This type of dyestuff had already been recommended for the dyeing oftextile materials, in particular with mordanting agents such asderivatives of transition metals (chromium dyestuffs); these metals areunusable in the field of hair dyeing because of the risks of breakage towhich they can give rise with subsequent treatments such as perming. Theuse of these compounds under the conditions of the dyeing of human hairhas never been considered.

The hydroxyanthraquinones used according to the present invention forthe coloration of human hair are more particularly characterised in thatthey correspond to the general formula: ##STR2## in which R₁, R₂, R₃,R₄, R₅, R₆, R₇ and R₈ independently of one another denote a hydrogenatom, a hydroxyl group, an alkyl group, an alkyl group substituted, forexample, by a hydroxyl, amino or acyl group, an alkoxy group, a nitrogroup, a halogen group, an SO₃ H, CHO, CO₂ H or SO₃ Na group or a --CO₂R' group, in which R' denotes alkyl or an alkali metal, with the provisothat: at least two of the groups R₁, R₂, R₃, R₄, R₅, R₆, R₇ and R₈denote hydroxyl, and that if R₁ and R₂ denote OH, R₅, R₆, R₇ and R₈denoting hydrogen, then at least one of the two groups R₃ and R₄ isdifferent from hydrogen, or alternatively if R₁ and R₃ denote OH, R₂ andR₄ denoting hydrogen and one or two of the substituents R₅, R₆, R₇ andR₈ denoting hydroxyl, then at least one of the substituents R₅, R₆, R₇and R₈ is different from hydrogen, alkyl or halogen.

The preferred alkyl groups have 1 to 4 carbon atoms and denote methyl orethyl, in particular.

The alkali metals which R' may represent are preferably sodium orpotassium.

The compounds which are more particularly preferred according to theinvention are the following compounds: 1,4-dihydroxyanthraquinone,1,2,4-trihydroxyanthraquinone, 1,2,7-trihydroxyanthraquinone,1,2,5,8-tetrahydroxyanthraquinone,3-carboxy-1,2,4-trihydroxyanthraquinone,2-carboxy-1-methyl-3,5,6,8-tetrahydroxyanthraquinone,3-sulpho-1,2,4-trihydroxyanthraquinone,3-sulpho-1,2-dihydroxyanthraquinone,5,8-dichloro-1,4-dihydroxyanthraquinone and1,8-dihydroxy-3-hydroxymethylanthraquinone.

Other compounds of particular value within the scope of the presentinvention are the following compounds:1,2-dihydroxy-4-nitroanthraquinone, 2-sulpho-1,4-dihydroxyanthraquinone,2,6-disulpho-1,4-dihydroxyanthraquinone,3-nitro-1,2,4-trihydroxyanthraquinone, 1,2,5-trihydroxyanthraquinone,3-sulpho-1,2,6-trihydroxyanthraquinone,3-nitro-1,2,6-trihydroxyanthraquinone,3-sulpho-1,2,7-trihydroxyanthraquinone,3-sulpho-1,4,5-trihydroxyanthraquinone,1,2,4,5,8-pentahydroxyanthraquinone,1,2,4,5,6,8-hexahydroxyanthraquinone,3,7-disulpho-1,2,4,5,6,8-hexahydroxyanthraquinone,1,2,4,5,7,8-hexahydroxyanthraquinone,3-nitro-1,2,4,5,7,8-hexahydroxyanthraquinone,2-methyl-1,3-dihydroxyanthraquinone,2-carboxy-1,3-dihydroxyanthraquinone,2-methyl-1,6-dihydroxyanthraquinone,6-methyl-1,2,5-trihydroxyanthraquinone,5-carboxy-1,2,4-trihydroxyanthraquinone,7-chloro-3-methyl-1,5,6,8-tetrahydroxyanthraquinone,2-carboxy-3-methyl-1,5,6,8-tetrahydroxyanthraquinone,3-methyl-1,2,4,7,8-pentahydroxyanthraquinone,3-methyl-1,2,5,6,7,8-hexahydroxyanthraquinone,3-methyl-6-methoxy-1,5,7,8-tetrahydroxyanthraquinone,1,2,6-trihydroxyanthraquinone and 1,8-dihydroxy-3-carboxyanthraquinone.

The class of the hydroxyanthraquinones is particularly rich in naturalcompounds, these compounds being, in particular,polyhydroxyanthraquinones which are unsubstituted or substituted bycarboxyl, halogen, alkyl or substituted alkyl groups.

Amongst the natural compounds belonging to the hydroxyanthraquinonesdefined above, the following may be mentioned more particularly:

                                      TABLE 1                                     __________________________________________________________________________     ##STR3##                                                                     SUBSTITUENTS                                                                  Common Name                                                                           R.sub.1 R.sub.2                                                                            R.sub.3                                                                              R.sub.4 R.sub.5                                                                           R.sub.6                                                                           R.sub.7                                                                           R.sub.8                                                                           Origin                    __________________________________________________________________________    3-Methyl-                                                                             OH      OH   CH.sub.3                       Digitalis spp.            alizarin                                                                      6-Methyl-                                                                             OH      OH                      CH.sub.3    Hymenodycten              alizarin                                            excelsum - Coprosma                                                           parviflora                Xanthopurpurin                                                                        OH           OH                             Rubia spp. - Gallium                                                          spp. etc.                 Rubiadine                                                                             OH      CH.sub.3                                                                           OH                             Rubiatinctorium -                                                             Morinda spp. -                                                                Coprosma spp.             Lucidine                                                                              OH      CH.sub.2 OH                                                                        OH                             Coprosma spp. -                                                               Asperula odorata          Nordamna-                                                                             OH      CHO  OH                             Morinda spp. -            canthal                                             Damnacanthus major        Munjistine                                                                            OH      COOH OH                             Rubia spp. - Rubia                                                            cordifolia munjista       Chrysophanol                                                                          OH           CH.sub.3                   OH  Rheum spp. - Rumex -                                                          Rhamnus spp.              2-Methyl-                                                                             OH      CH.sub.3    OH                      Tectona granois           quinizarin                                                                    Soranjidiol                                                                           OH      CH.sub.3                OH          Morinda spp. -                                                                Coprosma acerosa          Phomarin                                                                              OH           CH.sub.3           OH          Phoma foveata -                                                               Digitalis spp.            Aloe emodin                                                                           OH           CH.sub.2 OH                OH  Aloe spp. -                                                                   Asphodelus albus          Rhein   OH           COOH                       OH  Rheum spp. - Rumex                                                            spp. - Cassia spp.        Anthragallol                                                                          OH      OH   OH                             Coprosma lucida -         (and methyl                                                                           OH      OH   OCH.sub.3                      Rubia tinctorium          ethers) OCH.sub.3                                                                             OH   OH                                                               OH      OCH.sub.3                                                                          OH                                                       Purpurin                                                                              OH      OH          OH                      Rubia spp. - Gallium                                                          spp. - Asperula                                                               odorata                   Pseudopurpurin                                                                        OH      OH   COOH   OH                      Rubia spp. - Gallium                                                          spp. - Asperula spp.      Morindone                                                                             OH      CH.sub.3            OH  OH          Morinda spp. -                                                                Coprosma australis        Obtusifoline                                                                          OCH.sub.3                                                                             OH   CH.sub.3                   OH  Cassia obstusifolia       Juzunol OCH.sub.3                                                                             CH.sub.2 OH                                                                        OH             OH              Damnacanthus major        Norjuzunal                                                                            OH      CHO  OH             OH              Damnacanthus major        Juzunal OCH.sub.3                                                                             CHO  OH             OH              Damnacanthus spp.         Asperthecin                                                                           OH      OH   CH.sub.2 OH    OH  OH      OH  Aspergillus spp.          Macrosporin     CH.sub.3                                                                           OH             OH      OCH.sub.3                                                                             Altenaria spp.            Coelulatin                                                                            OH      CH.sub.2 OH                                                                        OH                         OH  Coelospermun                                                                  reticulatum               Physcion                                                                              OH           CH.sub.3           OCH.sub.3                                                                             OH  Rheum spp. -                                                                  Rumex spp.                Questin OH           CH.sub.3           OH      OCH.sub.3                                                                          Penicillium fre-                                                             quentans - Asper-                                                             gillus terreus            Questinol                                                                             OH           CH.sub.2 OH        OH      OCH.sub.3                                                                          Penicillium fre-                                                             quentans                  7-Chloroemodin                                                                        OH           CH.sub.3           OH  Cl  OH  Nephroma laevigatum-      (and methyl                                                                           OH           CH.sub. 3          OCH.sub.3                                                                         Cl  OH  Caloplaca spp.            ethers) OCH.sub.3    CH.sub.3           OH  Cl  OH                            5,7-Dichloro-                                                                         OH           CH.sub.3       Cl  OH  Cl  OH  Anaptychia                emodin                                              obscurata                 7-Chlorocitro-                                                                        OH           CH.sub.2 OH        OH  Cl  OH  Aspergillus               rosein                                              tumigatus                 Fallacinol                                                                            OH           CH.sub.2 OH        OCH.sub.3                                                                             OH  Teloschistes spp. -                                                           Xanthoria spp.            Carviolin                                                                             OCH.sub.3    CH.sub.2 OH        OH      OH  Penicillium                                                                   roseopupureum             Fallacinal                                                                            OH           CHO                OCH.sub.3                                                                             OH  Xanthoria spp. -                                                              Caloplaca spp.            Emodic acid                                                                           OH           COOH               OH      OH  Penicillium cyclopium                                                         -                                                                             Xanthoria parietina       Parietinic acid                                                                       OH           COOH               OCH.sub.3                                                                             OH  Xanthoria spp. -                                                              Caloplaca spp.            Endocrocin                                                                            OH      CO.sub.2 H                                                                         CH.sub. 3          OH      OH  Nephromopsis                                                                  endocrocea                Dermolutein                                                                           OH      COOH CH.sub.3           OH      OCH.sub.3                                                                         Dermocybe                 5-Chloro-                                                                             OH      COOH CH.sub.3       Cl  OH      OCH.sub.3                                                                         Dermocybe spp.            dermolutein                                                                   Dermocybin                                                                            OH           CH.sub.3       OH  OCH.sub.3                                                                         OH  OH  Cortinarius                                                                   sanguneus                 Nalgiovensin                                                                          OH                                                                                          ##STR4##          OCH.sub.3                                                                             OH  Penicillium nalgiovens                                                        is                        Nalgiolaxin                                                                           OH                                                                                          ##STR5##          OCH.sub.3                                                                         Cl  OH  Penicillium nalgiovens                                                        is                        Ptilometric                                                                           OH      COOH n-C.sub.3 H.sub.7  OH      OH  Ptilometra                acid                                                australis                 Islandicin                                                                            OH           CH.sub.3                                                                             OH                  OH  Penicillium spp.          Helmintho-                                                                            OH           CH.sub.3       OH          OH  Pyrenolora graminea                                                           -                         sporin                                              Helminthosporium                                                              spp.                      Digitopurpon                                                                          OH           CH.sub.3                                                                             OH      OH              Digitalis purpura         Copareolatin         CH.sub.3                                                                             OH          OH  OH  OH  Coprosma areolata         (and methyl                                                                   ethers)                                                                       7-Hydroxy-                                                                            OH           CH.sub.3           OH  OH  OH  Heliococcus confusus      emodin                                                                        Dermoglaucin                                                                          OH           CH.sub.3           OCH.sub.3                                                                         OH  OH  Cortinarius                                                                   sanguineus                Majoronal                                                                             OH      CHO  OH     OH      OCH.sub.3       Damnacanthus major        Isoerythro-                                                                           OH      OH   OH                 OH      CH.sub.3                                                                           Laccifer lacca           laccin                                                                        Cereoalbolinic                                                                        OH      OH   OH                 OH  COOH                                                                              CH.sub.3                                                                           Ceroplastes              acid                                                ulbolineatus              Kermesic acid                                                                         OH           OH     OH          OH  COOH                                                                              CH.sub.3                                                                           Kermococcus ilicis       Carminic acid                                                                         OH      Gluco-                                                                             OH     OH          OH  COOH                                                                              CH.sub.3                                                                           Dactylopius coccus                       side                                                          Laccaic acid D                                                                        OH           OH                 OH  COOH                                                                              CH.sub.3                                                                           Laccifer lacca           Xanthorin                                                                             OH           CH.sub.3       OH  CH.sub.3                                                                              OH  Xanthoria elegans -                                                           Laurera purpurina         Valsarin I                                                                            OH           CH.sub.3       OH  OH  Cl  OH  Valsaria rubricosa -                                                          Lasallia papulosa         Valsarin II                                                                           OH           CH.sub.3                                                                             OH          OH  Cl  OH  Valsaria rubricosa -                                                          Lasallia papulosa         Clavorubin                                                                            OH      COOH CH.sub.3       OH  OH      OH  Claviceps purpurea        (Nor)solorinic                                                                        CO(CH.sub.2).sub.4 CH.sub.3                                                           COC.sub.5 H.sub.11                                                                 OH                 OH      OH  Solorina crocea -         acid                                                Aspergillus                                                                   versicolor                2,5,7-Tri-                                                                            OH      OH   CH.sub.3       OH  OH  OH  OH  Mypcoblastus              hydroxyemodin                                       sanguinarius               Boletol                                                                               OH      OH          OH      COOH                                                                              ##STR6##                                                                              COOH                                                                              Boletus spp.             Dermorubin                                                                            OH      COOH CH.sub.3                                                                             OH          OH      OCH.sub.3                                                                         Dermocybe spp.            5-Chlorodermo-                                                                        OH      COOH CH.sub.3                                                                             OH      Cl  OH      OCH.sub.3                                                                         Dermocybe spp.            rubin                                                                         Erythroglaucin                                                                        OH           CH.sub.3                                                                             OH          OCH.sub.3                                                                             OH  Aspergillus spp. -                                                            Xanthoria elegans         Cynodontin                                                                            OH           CH.sub.3                                                                             OH      OH          OH  Helminthosporium                                                              spp.                              OH      CH.sub.3    OH      OH  CH.sub.3                                                                              OH  Curvularia spp. etc.      Aurantioobtusin                                                                       OCH.sub.3                                                                             OH   CH.sub.3           OH  OCH.sub.3                                                                         OH  Cassia obtusifolia        Obtusin OCH.sub.3                                                                             OH   CH.sub.3           OCH.sub.3                                                                         OCH.sub.3                                                                         OH  Cassia obtusifolia        6-Methyl ether                                                                        OH           OH     CO(CH.sub.2).sub.2 CH.sub.3                                                           OH  OCH.sub.3                                                                             OH  Comatula spp.             of rubro-                                                                     comatulin                                                                     Ventimalin                                                                            OH      OH   CH.sub.3                                                                             OH              OH  OH  Ventilago viminalis       Viminalin                                                                             OCH.sub.3                                                                             OH   CH.sub.3                                                                             OH              OH  OCH.sub.3                                                                          Ventilago                __________________________________________________________________________                                                        viminalis             

The natural compounds can be used, within the scope of the presentinvention, either as such in the form of their isolated molecules or, ifappropriate, in the form of C-glucosides or O-glucosides or in the formof extracts or plants in which they are present. The plants or plantextracts which are particularly preferred are those shown in Table 1above.

The dyeing compositions for human hair, according to the presentinvention, are thus essentially characterised in that they contain atleast one dyestuff corresponding to the formula (I) defined above, in acosmetically acceptable medium.

The compositions preferably contain these dyestuffs in proportions of0.005 to 10% by weight and preferably 0.01 to 7% by weight.

The compositions intended for dyeing human hair, according to theinvention, can be presented in various forms such as liquids, creams,gels, oils, powders or any other form suitable for dyeing the hair. Inparticular, they can be packaged in aerosol flasks, in the presence of apropellent.

These compositions can be used in the form of colouring setting lotions,in which case application is not followed by rinsing, or in the form ofcolouring shampoos, dyes or colouring poultices, in which casesapplication is followed by rinsing and, if appropriate, by shampooing.

A particularly preferred embodiment of the compositions according to theinvention is in the form of poultices. In this case, thehydroxyanthraquinones according to the invention, and preferably thehydroxyanthraquinones of natural origin, which can be in the differentforms mentioned above, are prepared in the form of a powder which isstable on storage, and are introduced into a solid medium which can be apowder, flour or a starchy or mucilaginous substance, and which isdiluted at the time of use with an appropriate liquid so as to form amixture having an appropriate consistency for application to the hair.

The powders used in the poultices according to the invention can beinsoluble substances such as silicas, plants, clays, plants pulverisedafter solvent extraction of their active principles, or plantscontaining the hydroxyanthraquinones of natural origin, according to theinvention. The liquid used to dilute the powder can be water and/or acosmetically acceptable solvent such as an alcohol, glycol or oil. Theviscosity generally obtained after mixing is from 300 to 3,500centipoises.

It is of course possible to introduce, in addition to thehydroxyanthraquinones of natural origin, other hydroxyanthraquinonesaccording to the invention and also other natural or syntheticdyestuffs. Other natural dyestuffs which may be mentioned in thisrespect are lawsone, juglone, indigo, and the plants or extracts inwhich these dyestuffs are present.

The cosmetically acceptable medium of the other embodiments of dyeingcompositions for human hair, according to the invention, is generallyaqueous, suitably having a pH from 2 to 11; it can be adjusted to thedesired value with the aid of alkalising agents such as ammonia, alkalimetal carbonates, alkanolamines such as mono-, di or tri-ethanolamine,and alkylamines, or acidifying agents such as hydrochloric acid,sulphuric acid or citric acid.

These compositions can also contain anionic, cationic, non-ionic and/oramphoteric surface-active agents or mixtures thereof. Amongst thepreferred surface-active agents, there may be mentioned, moreparticularly, soaps, alkylbenzenesulphonates,alkylnaphthalenesulphonates, sulphates, ether-sulphates and sulphonatesof fatty alcohols, quanternary ammonium salts such astrimethylcetylammonium bromide and cetylpyridinium bromide, fatty aciddiethanolamides, polyoxyethyleneated or polyglycerolated acids, alcoholsor amides, and polyoxyethyleneated or polyglycerolated alkylphenols. Thesurface-active agents are typically present in the compositionsaccording to the invention in proportions of 0.1 to 55% by weight andpreferably 1 to 40% by weight, relative to the total weight of thecomposition.

The compositions can also contain organic solvents for solubilisingcompounds which would not otherwise be sufficiently soluble in water.Examples of these solvents include lower alkanols such as ethanol andisopropanol, polyols such as glycerol, glycol or glycol ethers, such asethylene glycol monobutyl ether, ethylene glycol, propylene glycol, anddiethylene glycol monoethyl ether and monomethyl ether, and analogousproducts or mixtures thereof. These solvents are preferably used inproportions from 1 to 60% by weight and more particularly from 3 to 30%by weight, relative to the total weight of the composition.

The compositions can also contain anionic, non-ionic, cationic oramphoteric polymers, suitably in proportions from 0.1 to 5% by weight.

The compositions according to the invention can be thickened, preferablywith sodium alginate, gum arabic, cellulose derivatives such asmethylcellulose, hydroxyethylcellulose, hydroxypropylmethylcellulose andcarboxymethylcellulose, and various polymers serving this purpose, suchas acrylic acid derivatives. It is also possible to use inorganicthickeners such as bentonite. These thickeners are preferably present inproportions of 0.1 to 5% by weight and in particular 0.5 to 3% byweight, relative to the total weight of the composition.

Reducing agents and antioxidants, such as sodium sulphite, thioglycolicacid, thiolactic acid, sodium bisulphite, ascorbic acid andhydroquinone, can also be included in the compositions according to theinvention. These reducing agents and antioxidants are advantageouslypresent in the composition in proportions of 0.05 to 1.5% by weight,relative to the total weight of the composition.

Of course, any other adjuvants normally used in hair-dyeingcompositions, such as penetrating agents, sequestering agents, buffersand perfumes, can be included in the compositions according to theinvention.

It is self-evident that the compositions according to the invention canalso contain other direct dyestuffs, especially anthraquinone dyestuffsother than the hydroxyanthraquinones used in this invention, azodyestuffs, nitrobenzene derivatives, indophenols, indamines andindoanilines, and hydroxyl derivatives of benzaldehyde.

The compositions according to the invention can also contain so-calledoxidation dyestuffs, that is to say compounds which are not inthemselves dyestuffs, but which are converted to dyestuffs bycondensation in an oxidising medium. The oxidation dyestuffs aredivided, on the one hand, into oxidation dyestuff precursors of the paratype, generally diaminobenzenes, diaminopyridines and aminophenols, inwhich the functional groups are in the para-position relative to oneanother, and oxidation dyestuff precursors of the ortho type, in whichthe functional groups are in the ortho position relative to one another,and on the other hand, into compounds referred to as modifiers, tonersor couplers, which are so-called meta derivatives, generallymeta-diaminobenzenes, meta-diaminopyridines, meta-aminophenols,meta-diphenols and also phenols.

These compositions can also contain so-called "rapid" oxidationdyestuffs, which are dyestuff precursors of the benzene series whichcontain, on the nucleus, three substituents which are hydroxyl, methoxyor amino groups and which are capable of oxidising directly in air.

The dyestuffs are preferably present in proportions from 0.005 to 10% byweight.

Particularly advantageous results can be obtained for the compositionsdefined above containing polyhydroxyanthraquinones which areunsubstituted or substituted by non-acidic groups and which preferablyhave alkaline pH values from 7 to 12.

If the compositions according to the invention containpolyhydroxyanthraquinones substituted by acid groups such as carboxyl orsulphonic acid groups, particularly advantageous results are obtainedfor acid pH values of 2 to 7.

The hair-dyeing process according to the invention is essentiallycharacterised in that at least one composition of this invention isapplied to the hair, before or after shampooing, and left on the hairfor, say, 5 to 60 minutes and preferably 5 to 40 minutes, and the hairis rinsed and dried. A composition in the form of a setting lotion canalso be applied to the hair, after shampooing, and the hair is thendried.

The coloration of the hair can also be carried out according toprocesses comprising several steps, at least one of which consist inapplying a dyestuff of the formula (I). These multi-step processes canuse compositions having different pH values according to the nature ofthe dyestuffs present. Within the scope of the invention, it ispossible, in particular, to envisage multi-step dyeing using first acomposition containing polyhydroxyanthraquinones with acidic groups andhaving a pH of 2 to 7, and, in a second step, a composition containing apolyhydroxyanthraquinone having an alkaline pH of 7 to 12 or vice versa.

The following Examples further illustrate the present invention.

EXAMPLE 1

The following composition is prepared:

    ______________________________________                                        1,2,4-Trihydroxyanthraquinone                                                                         1      g                                              Lanette wax O           20     g                                              Copra monoethanolamide  5      g                                              SIPON LA 30             10     g                                              2-Amino-2-methylpropanol q.s.p.                                                                       pH     10                                             Distilled water q.s.p.  100    g                                              ______________________________________                                    

This composition is a claret-coloured cream.

When applied to a natural chestnut head of hair for 30 minutes, itimparts to the hair, after rinsing, shampooing and drying, a veryluminous mahogany-red sheen.

EXAMPLE 2

The following composition is prepared:

    ______________________________________                                        1,2,4,-Trihydroxy-3-carboxyanthraquinone                                                            0.05      g                                             Vinyl acetate/crotonic acid                                                                         1.8       g                                             (90/10) copolymer                                                             Vinylpyrrolidone/vinyl acetate                                                                      0.4       g                                             (60/40) copolymer                                                             96° strength ethyl alcohol q.s.p.                                                            50° alcoholic strength                           Triethanolamine q.s.p pH 6                                                    Distilled water q.s.p 100       g                                             ______________________________________                                    

This purple setting lotion is applied to a deep blond head of hair.After shaping and drying, the hair is embellished with an iridiscentsheen.

EXAMPLE 3

The following composition is prepared:

    ______________________________________                                        Sodium salt of 1,2-dihydroxy-3-                                                                        1.0    g                                             sulphoanthraquinone monohydrate                                               Lawsone                  0.3    g                                             Cetyl alcohol            17.0   g                                             MERGITAL CS 15/E         6.0    g                                             Oleyl alcohol            3.0    g                                             Citric acid q.s.         pH     3                                             Distilled water q.s.p.   100    g                                             ______________________________________                                    

This yellow-coloured cream is applied to light chestnut hair.

After an interval of 20 minutes, followed by rinsing, the head of pairpossesses a deep coppery-red sheen.

EXAMPLE 4

The following composition is prepared:

    ______________________________________                                        1,2,5,8-Tetrahydroxyanthraquinone                                                                      0.7    g                                             1,4-Dihydroxyanthraquinone                                                                             1.3    g                                             Lanette wax O            20.0   g                                             Copra monoethanolamide   5.0    g                                             SIPON LA 30              10.0   g                                             2-Amino-2-methylpropanol q.s.                                                                          pH     9.6                                           Distilled water q.s.p    100    g                                             ______________________________________                                    

This composition constitutes a purplish-blue/brown-coloured cream.

It is applied to a chestnut head of hair for 30 minutes.

After rinsing, shampooing and drying, the hair possesses an ashen sheen.

EXAMPLE 5

The following composition is prepared:

    ______________________________________                                        1-Methyl-2-carboxy-3,5,6,8-tetra-                                                                       0.6    g                                            hydroxyanthraquinone                                                          3-Carboxy-1,2,4-trihydroxyanthraquinone                                                                 0.3    g                                            Cetyl alcohol             17.0   g                                            MERGITAL CS 15/E          6.0    g                                            Oleyl alcohol             3.0    g                                            Citric acid q.s           pH     2.7                                          Distilled water q.s.p     100    g                                            ______________________________________                                    

This carmine-coloured cream is applied to light chestnut hair for 30minutes.

After rinsing, shampooing and drying, this hair is shaded with apurple-violet sheen.

EXAMPLE 6

The following composition is prepared:

    ______________________________________                                        1,2,5,8-Tetrahydroxyanthraquinone                                                                      0.6    g                                             1-N--(β-Hydroxyethyl)-amino-2-                                                                    0.2    g                                             methoxy-4-nitrobenzene                                                        1-N--(β-Hydroxyethyl)-amino-3-nitro-                                                              0.1    g                                             4-aminobenzene                                                                SACTIPON 8533            25.0   g                                             Coconut fatty acid diethanolamide                                                                      5.0    g                                             2-Butoxyethanol          1.0    g                                             Monethanolamine q.s      pH     9.6                                           Distilled water q.s.p    100    g                                             ______________________________________                                    

This foaming liquid, which has a deep violet-brown colour, is acolouring shampoo.

It is applied to a light chestnut head of hair containing a considerablepercentage of white hair.

After an interval of 15 minutes, followed by rinsing, the hair iscoloured in an ashen, light chestnut shade and the white hair is coveredwith the same tint.

EXAMPLE 7

The following composition is prepared:

    ______________________________________                                        Sodium salt of 1,2-dihydroxy-3-sulpho-                                                              0.1       g                                             anthraquinone monohydrate                                                     Vinyl acetate/crotonic acid                                                                         1.8       g                                             (90/10) copolymer                                                             Vinylpyrrolidone/vinyl acetate                                                                      0.4       g                                             (60/40) copolymer                                                             96° strength ethyl alcohol q.s.p                                                             50° alcoholic strength                           Triethanolamine q.s.  pH 5                                                    Distilled water q.s.p.                                                                              100       g                                             ______________________________________                                    

This composition constitutes a setting lotion, which is applied to ablond head of hair.

After shaping and drying, the hair possesses a pearlescent golden sheen.

EXAMPLE 8

The following composition is prepared:

    ______________________________________                                        1,2,7-Trihydroxhanthraquinone                                                                          0.4    g                                             1-Amino-2-nitro-4-hydroxybenzene                                                                       0.1    g                                             1-N--(β-Hydroxyethyl)-amino-2-                                                                    0.3    g                                             nitro-4-hydroxybenzene                                                        Lanette wax O            20.0   g                                             Copra monoethanolamide   5.0    g                                             SIPON LA 30              10.0   g                                             2-Amino-2-methylpropanol q.s.p.                                                                        pH     9.9                                           Distilled water q.s.p.   100    g                                             ______________________________________                                    

This red-brown cream is applied to deep chestnut hair.

After 30 minutes, the product is rinsed out.

After shampooing and drying, a head of hair dyed with an intense anddeep coppery-red sheen is obtained.

EXAMPLE 9

The following composition is prepared:

    ______________________________________                                        1,2,4-Trihydroxyanthraquinone                                                                           0.05   g                                            1,2,5,8-Tetrahydroxyanthraquinone                                                                       0.3    g                                            Para-toluylenediamine dihydrochloride                                                                   0.5    g                                            Para-aminophenol          0.1    g                                            Meta-aminophenol          0.1    g                                            Resorcinol                0.4    g                                            Hydroquinone              0.15   g                                            SINNOPAL NP9              22.0   g                                            SINNOPAL NP4              22.0   g                                            Propylene glycol          11.0   g                                            96° strength ethyl alcohol                                                                       8.0    g                                            35° B strength sodium bisulphite solution                                                        1.3    g                                            Pentasodium salt of diethylenetriamine-                                                                 2.4    g                                            pentaacetic acid                                                              22° B strength ammonia solution                                                                  10.2   g                                            Distilled water q.s.p.    100    g                                            ______________________________________                                    

On dilution with an equal weight of hydrogen peroxide of 20 volumesstrength, this black-violet liquid composition gives a gel, which isapplied to a deep blond head of hair for 30 minutes.

After rinsing and shampooing, the hair is coloured in an ashen, lightblond shade.

EXAMPLE 10

The following composition is prepared:

    ______________________________________                                        1-Methyl-2-carboxy-3,5,6,8-                                                                            5.0    g                                             tetrahydroxyanthraquinone                                                     Juglone                  1.0    g                                             Rye flour                15.0   g                                             Pulverised frangula      15     g                                             Pulverised horse-chestnut leaves                                                                       60.0   g                                             Citric acid              4.0    g                                             ______________________________________                                    

This yellowish powder is mixed with 3.5 times its weight of warm waterat the time of use. The mixture obtained, which has a pH of 3.3 and abrick-red colour, has the consistency of a poultice.

When applied to blond hair for 20 minutes, it imparts to the hair, afterrinsing and shampooing, a luminous golden sheen.

EXAMPLE 11

    ______________________________________                                        5,8-Dichloro-1,4-dihydroxyanthraquinone                                                                 0.7    g                                            Lanette wax O             20     g                                            Copra monoethanolamide    5      g                                            Sipon LA 30               10     g                                            2-Amino-2-methylpropan-1-ol q.s.p.                                                                      pH = 9.5                                            Distilled water q.s.p.    100     g                                           ______________________________________                                    

This composition is a red-coloured cream. When applied to light blondhair for 30 minutes, it imparts to the hair, after rinsing, shampooingand drying, a pearlescent sheen.

EXAMPLE 12

    ______________________________________                                        1,8-Dihydroxy-3-hydroxymethylanthraquinone                                                               2     g                                            Powdered saponaria         30    g                                            Maize cobs                 50    g                                            Wheat flour                8     g                                            Anhydrous sodium carbonate 10    g                                            ______________________________________                                    

This beige-coloured powder is mixed with three times its weight of warmwater at the time of use; the mixture thus obtained, which has agreen-brown colour and a pH of 9.8, has the consistency of a poultice.

When applied to blond hair for 30 minutes, it imparts to the hair, afterrinsing and drying, a coppery-beige sheen.

The various tradenames used in the foregoing examples are explained ingreater detail below:

Lanette wax O: 50/50 mixture of cetyl alcohol and stearyl alcohol, soldby HENKEL

SIPON LA 30: 20% strength solution of ammonium lauryl-sulphate, sold byHENKEL

MERGITAL CS15/E: Cetyl-stearyl alcohol containing 15 mols of ethyleneoxide, sold by HENKEL

SACTIPON 8533: Sodium salt of sulphated oxyethyleneated alkanol, sold byLEVER

SINNOPAL NP4: Nonylphenol oxyethyleneated with 4 mols of ethylene oxide,sold by HENKEL.

SINNOPAL NP 9: Nonylphenol oxyethyleneated with 9 mols of ethyleneoxide, sold by HENKEL.

We claim:
 1. A composition for dyeing human hair comprising in anaqueous medium for application to said hair 0.005 to 10 percent byweight of said composition of a compound of the formula ##STR7## whereinR₁, R₂, R₃, R₄, R₅, R₆, R₇ and R₈ each independently represent hydrogen,hydroxyl, alkyl having 1-4 carbon atoms, alkyl having 1-4 carbon atomsand substituted by hydroxy, amino, acyl, halogen, SO₃ H, CHO, SO₃ Na or--CO₂ R¹ wherein R¹ represents alkyl having 1-4 carbon atoms or alkalimetal, or said hydroxyanthraquinone is in the form of a glucoside, withthe provisos that(i) at least two of R₁, R₂, R₃, R₄, R₅, R₆, R₇ and R₈represent hydroxyl, (ii) if R₁ and R₂ represent OH, and R₅, R₆, R₇ andR₈ represent hydrogen, then at least one of R₃ and R₄ is other thanhydrogen, and (ii) if R₁ and R₃ represent OH, R₂ and R₄ representhydrogen and one or two of R₅, R₆, R₇ and R₈ represent hydroxyl, then atleast one of R₅, R₆, R₇ and R₈ is other than said hydrogen, alkyl orhalogen.
 2. The composition of claim 1 which also contains asurface-active agent in an amount of 0.1 to 55 percent by weightrelative to the total weight of said composition.
 3. The composition ofclaim 1 which also includes a lower alkanol, glycerol or glycol ether,or a mixture thereof in an amount of 1 to 60 percent by weight relativeto the total weight of said composition.
 4. The composition of claim 1which also includes, as a thickener, sodium alginate, gum arabic, methylcellulose, hydroxyethyl cellulose, hydroxypropylmethyl cellulose orcarboxymethyl cellulose, in an amount of 0.1 to 5 percent by weightrelative to the total weight of said composition.
 5. The composition ofclaim 1 which also includes, as a reducing agent and antioxidant, sodiumsulphite, thioglycolic acid, thiolactic acid, sodium bisulphite,ascorbic acid or hydroquinone, in an amount of 0.05 to 1.5 percent byweight relative to the total weight of said composition.
 6. Thecomposition of claim 1 wherein R₁ to R₈ represent hydrogen, chlorine,hydroxyl, alkyl, hydroxyalkyl, SO₃ H, CO₂ H or CHO.
 7. The compositionof claim 1 wherein said compound is selected from the group consistingof 1,4-dihydroxyanthraquinone, 1,2,4-trihydroxyanthraquinone,1,2,7-trihydroxyanthraquinone, 1,2,5,8-tetrahydroxyanthraquinone,3-carboxy-1,2,4-trihydroxyanthraquinone,2-carboxy-1-methyl-3,5,6,8-tetrahydroxyanthraquinone,3-sulpho-1,2-dihydroxyanthraquinone,3-sulpho-1,2,4-trihydroxyanthraquinone,5,8-dichloro-1,4-dihydroxyanthraquinone and1,8-dihydroxy-3-hydroxymethylanthraquinone.
 8. A composition accordingto claim 1 in which the hydroxyanthraquinone is selected from the groupconsisting of 2-sulpho-1,4-dihydroxyanthraquinone,2,6-disulpho-1,4-dihydroxyanthraquinone, 1,2,5-trihydroxyanthraquinone,3-sulpho-1,2,6-trihydroxyanthraquinone,3-sulpho-1,2,7-trihydroxyanthraquinone,3-sulpho-1,4,5-trihydroxyanthraquinone,1,2,4,5,8-pentahydroxyanthraquinone,1,2,4,5,6,8-hexahydroxyanthraquinone,3,7-disulpho-1,2,4,5,6,8-hexahydroxyanthraquinone,1,2,4,5,7,8-hexahydroxyanthraquinone,2-methyl-1,3-dihydroxyanthraquinone,2-carboxy-1,3-dihydroxyanthraquinone,2-methyl-1,6-dihydroxyanthraquinone,6-methyl-1,2,5-trihydroxyanthraquinone,5-carboxy-1,2,4-trihydroxyanthraquinone,7-chloro-3-methyl-1,5,6,8-tetrahydroxyanthraquinone,2-carboxy-3-methyl-1,5,6,8-tetrahydroxyanthraquinone,3-methyl-1,2,4,7,8-pentahydroxyanthraquinone,1,2,6-trihydroxyanthraquinone, 1,8-dihydroxy-3-carboxyanthraquinone and3-methyl-1,2,5,6,7,8-hexahydroxyanthraquinone.
 9. The composition ofclaim 1 which has a pH from 7 to
 12. 10. The composition of claim 1which has a pH from 2 to
 7. 11. A process for dyeing human haircomprises applying to said hair the composition of claim 1, permittingsaid composition to remain in contact with the hair for 5 to 60 minutesand then rinsing said hair.
 12. The process of claim 11 which includesdrying the rinsed hair.
 13. A composition for dyeing human haircomprising in an aqueous medium for application to said hair 0.005 to 10percent by weight of said composition of a compound of the formula##STR8## wherein R₁, R₂, R₃, R₄, R₅, R₆, R₇ and R₈ each independentlyrepresent hydrogen, hydroxyl, alkyl having 1-4 carbon atoms, alkylhaving 1-4 carbon atoms and substituted by hydroxy, amino, acyl,halogen, SO₃ H, CHO, CO₂ H, SO₃ Na or --CO₂ R¹ wherein R¹ representsalkyl having 1-4 carbon atoms or alkali metal, with the provisos that(i)at least two of R₁, R₂, R₃, R₄, R₅, R₆, R₇ and R₈ represent hydroxyl,(ii) if R₁ and R₂ represent OH, and R₅, R₆, R₇ and R₈ representhydrogen, then at least one of R₃ and R₄ is other than hydrogen, and(iii) if R₁ and R₃ represent OH, R₂ and R₄ represent hydrogen and one ortwo of R₅, R₆, R₇ and R₈ represent hydroxyl, then at least one of R₅,R₆, R₇ and R₈ is other than said hydrogen, alkyl or halogen.
 14. Thecomposition of claim 13 wherein said alkali metal is sodium orpotassium.
 15. A composition for dyeing human hair comprising in anaqueous medium for application to said hair 0.005 to 10 percent byweight of said composition of a compound of the formula ##STR9## whereinthe combinations of R₁ to R₈ are selected from the group consistingof(1) R₁ and R₂ are each OH, R₃ is CH₃ and R₄, R₅, R₆, R₇ and R₈ areeach hydrogen, (2) R₁ and R₂ are each OH, R₆ is CH₃ and R₃, R₄, R₅, R₇and R₈ are each hydrogen, (3) R₁ and R₃ are each OH and R₂, R₄, R₅, R₆,R₇ and R₈ are each hydrogen, (4) R₁ and R₃ are each OH, R₂ is CH₃ andR₄, R₅, R₆, R₇ and R₈ are each hydrogen, (5) R₁ and R₃ are each OH, R₂is CH₂ OH and R₄, R₅, R₆, R₇ and R₈ are each hydrogen, (6) R₁ and R₃ areeach OH, R₂ is CHO and R₄, R₅, R₆, R₇ and R₈ are each hydrogen, (7) R₁and R₃ are each OH, R₂ is COOH and R₄, R₅, R₆, R₇ and R₈ are eachhydrogen, (8) R₁ and R₈ are each OH, R₃ is CH₃ and R₂, R₄, R₅, R₆ and R₇are each hydrogen, (9) R₁ and R₄ are each OH, R₂ is CH₃ and R₃, R₅, R₆,R₇ and R₈ are each hydrogen, (10) R₁ and R₆ are each OH, R₂ is CH₃ andR₃, R₄, R₅, R₇ and R₈ are each hydrogen, (11) R₁ and R₆ are each OH, R₃is CH₃ and R₂, R₄, R₅, R₇ and R₈ are each hydrogen, (12) R₁ and R₈ areeach OH, R₃ is CH₂ OH and R₂, R₄, R₅, R₆ and R₇ are each hydrogen, (13)R₁ and R₈ are each OH, R₃ is COOH and R₂, R₄, R₅, R₆ and R₇ are eachhydrogen, (14) R₁, R₂ and R₃ are each OH and R₄, R₅, R₆, R₇ and R₈ areeach hydrogen, (15) R₁, R₂ and R₄ are each OH and R₃, R₅, R₆, R₇ and R₈are each hydrogen, (16) R₁, R₂ and R₄ are each OH, R₃ is COOH and R₅,R₆, R₇ and R₈ are each hydrogen, (17) R₁, R₅ and R₆ are each OH, R₂ isCH₃ and R₃, R₄, R₇ and R₈ are each hydrogen, (18) R₁, R₃ and R₅ are eachOH, R₂ is CHO and R₄, R₆, R₇ and R₈ are each hydrogen, (19) R₁, R₂, R₅,R₆ and R₈ are each OH, R₃ is CH₂ OH and R₄ and R₇ are each hydrogen,(20) R₁, R₃ and R₈ are each OH, R₂ is CH₂ OH and R₄, R₅, R₆ and R₇ areeach hydrogen, (21) R₁, R₆ and R₈ are each OH, R₃ is CH₃, R₇ is Cl andR₂, R₄ and R₅ are each hydrogen, (22) R₁, R₆ and R₈ are each OH, R₃ isCH₃, R₅ and R₇ are each Cl and R₂ and R₄ are each hydrogen, (23) R₁, R₆and R₈ are each OH, R₃ is CH₂ OH, R₇ is Cl and R₂, R₄ and R₅ are eachhydrogen, (24) R₁, R₆ and R₈ are each OH, R₃ is COOH and R₂, R₄, R₅ andR₇ are each hydrogen, (25) R₁, R₆ and R₈ are each OH, R₂ is COOH, R₃ isCH₃ and R₄, R₅ and R₇ are each hydrogen, (26) R₁, R₆ and R₈ are each OH,R₂ is COOH, R₃ is n--C₃ H₇ and R₄, R₅ and R₇ are each hydrogen, (27) R₁,R₄ and R₈ are each OH, R₃ is CH₃ and R₂, R₅, R₆ and R₇ are eachhydrogen, (28) R₁, R₅ and R₈ are each OH, R₃ is CH₃ and R₂, R₄, R₆ andR₇ are each hydrogen, (29) R₁, R₄ and R₅ are each OH, R₃ is CH₃ and R₂,R₆, R₇ and R₈ are each hydrogen, (30) R₄, R₆, R₇ and R₈ are each OH, R₃is CH₃ and R₁, R₂ and R₅ are each hydrogen, (31) R₁, R₆, R₇ and R₈ areeach OH, R₃ is CH₃ and R₂, R₄ and R₅ are each hydrogen, (32) R₁, R₂, R₃and R₆ are each OH, R₈ is CH₃ and R₄, R₅ and R₇ are each hydrogen, (33)R₁, R₂, R₃ and R₆ are each OH, R₇ is COOH, R₈ is CH₃ and R₄ and R₅ areeach hydrogen, (34) R₁, R₃, R₄ and R₆ are each OH, R₇ is COOH, R₈ is CH₃and R₂ and R₅ are each hydrogen, (35) R₁, R₃, R₄ and R₆ are each OH, R₂is glucoside, R₇ is COOH, R₈ is CH₃ and R₅ is hydrogen, (36) R₁, R₃ andR₆ are OH, R₇ is COOH, R₈ is CH₃ and R₂, R₄ and R₅ are each hydrogen,(37) R₁, R₅ and R₈ are each OH, R₃ and R₆ are each CH₃ and R₂, R₄ and R₇are each hydrogen, (38) R₁, R₅, R₆ and R₈ are each OH, R₃ is CH₃, R₇ isCl and R₂ and R₄ are each hydrogen, (39) R₁, R₄, R₆ and R₈ are each OH,R₃ is CH₃, R₇ is Cl and R₂ and R₅ are each hydrogen, (40) R₁, R₅, R₆ andR₈ are each OH, R₂ is COOH, R₃ is CH₃ and R₄ and R₇ are each hydrogen,(41) R₃, R₆ and R₈ are each OH, R₁ is CO(CH₂)₄ CH₃, R₂ is COC₅ H₁₁ andR₄, R₅ and R₇ are each hydrogen, (42) R₁, R₂, R₅, R₆, R₇ and R₈ are eachOH, R₃ is CH₃ and R₄ is hydrogen, (43) R₁, R₂ and R₄ are OH, one of R₅and R₈ is COOH and the other is hydrogen and R₃, R₆ and R₇ are eachhydrogen, (44) R₁, R₄, R₅ and R₈ are each OH, R₃ is CH₃ and R₂, R₆ andR₇ are each hydrogen, (45) R₁, R₄, R₅, R₈ are each OH, R₂ and R₆ areeach CH₃ and R₃ and R₇ are each hydrogen, and (46) R₁, R₂, R₄, R₇ and R₈are each OH, R₃ is CH₃ and R₅ and R₆ are each hydrogen.
 16. Acomposition for dyeing human hair comprising in a solid carrier from0.005 to 10 weight percent of a compound of the formula ##STR10##wherein the combinations of R₁ to R₈ are selected from the groupconsisting of(1) R₁ and R₂ are each OH, R₃ is CH₃ and R₄, R₅, R₆, R₇ andR₈ are each hydrogen, (2) R₁ and R₂ are each OH, R₆ is CH₃ and R₃, R₄,R₅, R₇ and R₈ are each hydrogen, (3) R₁ and R₃ are each OH and R₂, R₄,R₅, R₆, R₇ and R₈ are each hydrogen, (4) R₁ and R₃ are each OH, R₂ isCH₃ and R₄, R₅, R₆, R₇ and R₈ are each hydrogen, (5) R₁ and R₃ are eachOH, R₂ is CH₂ OH and R₄, R₅, R₆, R₇ and R₈ are each hydrogen, (6) R₁ andR₃ are each OH, R₂ is CHO and R₄, R₅, R₆, R₇ and R₈ are each hydrogen,(7) R₁ and R₃ are each OH, R₂ is COOH and R₄, R₅, R₆, R₇ and R₈ are eachhydrogen, (8) R₁ and R₈ are each OH, R₃ is CH₃ and R₂, R₄, R₅, R₆ and R₇are each hydrogen, (9) R₁ and R₄ are each OH, R₂ is CH₃ and R₃, R₅, R₆,R₇ and R₈ are each hydrogen, (10) R₁ and R₆ are each OH, R₂ is CH₃ andR₃, R₄, R₅, R₇ and R₈ are each hydrogen, (11) R₁ and R₆ are each OH, R₃is CH₃ and R₂, R₄, R₅, R₇ and R₈ are each hydrogen, (12) R₁ and R₈ areeach OH, R₃ is CH₂ OH and R₂, R₄, R₅, R₆ and R₇ are each hydrogen, (13)R₁ and R₈ are each OH, R₃ is COOH and R₂, R₄, R₅, R₆ and R₇ are eachhydrogen, (14) R₁, R₂ and R₃ are each OH and R₄, R₅, R₆, R₇ and R₈ areeach hydrogen, (15) R₁, R₂ and R₄ are each OH and R₃, R₅, R₆, R₇ and R₈are each hydrogen, (16) R₁, R₂ and R₄ are each OH, R₃ is COOH and R₅,R₆, R₇ and R₈ are each hydrogen, (17) R₁, R₅ and R₆ are each OH, R₂ isCH₃ and R₃, R₄, R₇ and R₈ are each hydrogen, (18) R₁, R₃ and R₅ are eachOH, R₂ is CHO and R₄, R₆, R₇ and R₈ are each hydrogen, (19) R₁, R₂, R₅,R₆ and R₈ are each OH, R₃ is CH₂ OH and R₄ and R₇ are each hydrogen,(20) R₁, R₃ and R₈ are each OH, R₂ is CH₂ OH and R₄, R₅, R₆ and R₇ areeach hydrogen, (21) R₁, R₆ and R₈ are each OH, R₃ is CH₃, R₇ is Cl andR₂, R₄ and R₅ are each hydrogen, (22) R₁, R₆ and R₈ are each OH, R₃ isCH₃, R₅ and R₇ are each Cl and R₂ and R₄ are each hydrogen, (23) R₁, R₆and R₈ are each OH, R₃ is CH₂ OH, R₇ is Cl and R₂, R₄ and R₅ are eachhydrogen, (24) R₁, R₆ and R₈ are each OH, R₃ is COOH and R₂, R₄, R₅ andR₇ are each hydrogen, (25) R₁, R₆ and R₈ are each OH, R₂ is COOH, R₃ isCH₃ and R₄, R₅ and R₇ are each hydrogen, (26) R₁, R₆ and R₈ are each OH,R₂ is COOH, R₃ is n--C₃ H₇ and R₄, R₅ and R₇ are each hydrogen, (27) R₁,R₄ and R₈ are each OH, R₃ is CH₃ and R₂, R₅, R₆ and R₇ are eachhydrogen, (28) R₁, R₅ and R₈ are each OH, R₃ is CH₃ and R₂, R₄, R₆ andR₇ are each hydrogen, (29) R₁, R₄ and R₅ are each OH, R₃ is CH₃ and R₂,R₆, R₇ and R₈ are each hydrogen, (30) R₄, R₆, R₇ and R₈ are each OH, R₃is CH₃ and R₁, R₂ and R₅ are each hydrogen, (31) R₁, R₆, R₇ and R₈ areeach OH, R₃ is CH₃ and R₂, R₄ and R₅ are each hydrogen, (32) R₁, R₂, R₃and R₆ are each OH, R₈ is CH₃ and R₄, R₅ and R₇ are each hydrogen, (33)R₁, R₂, R₃ and R₆ are each OH, R₇ is COOH, R₈ is CH₃ and R₄ and R₅ areeach hydrogen, (34) R₁, R₃, R₄ and R₆ are each OH, R₇ is COOH, R₈ is CH₃and R₂ and R₅ are each hydrogen, (35) R₁, R₃, R₄ and R₆ are each OH, R₂is glucoside, R₇ is COOH, R₈ is CH₃ and R₅ is hydrogen, (36) R₁, R₃ andR₆ are OH, R₇ is COOH, R₈ is CH₃ and R₂, R₄ and R₅ are each hydrogen,(37) R₁, R₅ and R₈ are each OH, R₃ and R₆ are each CH₃ and R₂, R₄ and R₇are each hydrogen, (38) R₁, R₅, R₆ and R₈ are each OH, R₃ is CH₃, R₇ isCl and R₂ and R₄ are each hydrogen, (39) R₁, R₄, R₆ and R₈ are each OH,R₃ is CH₃, R₇ is Cl and R₂ and R₅ are each hydrogen, (40) R₁, R₅, R₆ andR₈ are each OH, R₂ is COOH, R₃ is CH₃ and R₄ and R₇ are each hydrogen,(41) R₃, R₆ and R₈ are each OH, R₁ is CO(CH₂)₄ CH₃, R₂ is COC₅ H₁₁ andR₄, R₅ and R₇ are each hydrogen, (42) R₁, R₂, R₅, R₆, R₇ and R₈ are eachOH, R₃ is CH₃ and R₄ is hydrogen, (43) R₁, R₂ and R₄ are OH, one of R₅and R₈ is COOH and the other is hydrogen and R₃, R₆ and R₇ are eachhydrogen, (44) R₁, R₄, R₅ and R₈ are each OH, R₃ is CH₃ and R₂, R₆ andR₇ are each hydrogen, (45) R₁, R₄, R₅, R₈ are each OH, R₂ and R₆ areeach CH₃ and R₃ and R₇ are each hydrogen, and (46) R₁, R₂, R₄, R₇ and R₈are each OH, R₃ is CH₃ and R₅ and R₆ are each hydrogen, said solidcarrier being a powder, flour or a starch or mucilaginous substance. 17.The composition of claim 16 wherein said compound is1-methoxy-2-carboxy-3,5,6,8-tetrahydroxy-anthraquinone.
 18. Thecomposition of claim 16 wherein said compound is1,8-dihydroxy-3-hydroxymethyl anthraquinone.
 19. A process for dyeinghuman hair comprising admixing the composition of claim 16 with a liquidso that the resulting admixture has a viscosity from 300 to 3,500centipoises, said liquid being water, an alcohol, glycol or oil,applying the resulting admixture to said hair and permitting saidadmixture to remain in contact with said hair for a period of timeranging from 5 to 60 minutes.
 20. The process of claim 19 which includesrinsing the hair subsequent to contact of said composition with saidhair for said period of time.
 21. The process of claim 19 which includeswashing the hair subsequent to contact of said composition for saidperiod of time.
 22. The process of claim 19 which includes rinsing andwashing the hair subsequent to contact of said composition with saidhair for said period of time.